Synergistic weed control from applications of aminocyclopyrachlor and clopyralid

ABSTRACT

Disclosed herein are herbicidal compositions comprising a synergistically herbicidal effective amount of (a) aminocyclopyrachlor, or an agriculturally acceptable salt or ester thereof, and (b) clopyralid, or an agriculturally acceptable salt or ester thereof. Also disclosed herein are methods of controlling undesirable vegetation, which comprise applying to vegetation or an area adjacent the vegetation or applying to soil or water to prevent the emergence or growth of vegetation (a) aminocyclopyrachlor, or an agriculturally acceptable salt or ester thereof, and (b) clopyralid, or an agriculturally acceptable salt or ester thereof, wherein (a) and (b) are each added in an amount sufficient to produce a synergistic herbicidal effect.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent ApplicationNo. 61/696,478, filed Sep. 4, 2012, which is incorporated herein byreference in its entirety.

FIELD OF THE DISCLOSURE

The present disclosure relates to herbicidal compositions comprising asynergistically herbicidal effective amount of (a) aminocyclopyrachloror an agriculturally acceptable salt or ester thereof, and (b)clopyralid or an agriculturally acceptable salt or ester thereof. Thepresent disclosure also relates to methods for controlling undesirablevegetation.

BACKGROUND

Many recurring problems in agriculture involve controlling growth ofundesirable vegetation that can, for instance, inhibit crop growth. Tohelp control undesirable vegetation, researchers have produced a varietyof chemicals and chemical formulations effective in controlling suchunwanted growth. However, a continuing need exists for new compositionsand methods to control growth of undesirable vegetation.

SUMMARY OF THE DISCLOSURE

Herbicides of many types have been disclosed in the literature and anumber are in commercial use. In some cases, herbicidal activeingredients have been found more effective in combination than whenapplied individually and this is referred to as “synergy” or“synergism.” The present disclosure is based on the discovery that (a)aminocyclopyrachlor, or an agriculturally acceptable salt or esterthereof, and (b) clopyralid, or an agriculturally acceptable salt orester thereof, display a synergistic herbicidal effect when applied incombination.

Accordingly, the present disclosure relates to herbicidal compositionscomprising a synergistically herbicidal effective amount of (a)aminocyclopyrachlor, or an agriculturally acceptable salt or esterthereof, and (b) clopyralid, or an agriculturally acceptable salt orester thereof. In some embodiments, (a) includes aminocyclopyrachlor inacid form. In some embodiments, (b) includes clopyralid-olamine. Theacid equivalent weight ratio of (a) to (b) can be from 1:70 to 12:1(e.g., from 1:4 to 1:2). In some embodiments, the composition furthercomprises an additional pesticide (e.g., aminopyralid, amicarbazone,bromoxynil, chlorsulfuron, 2,4-D, dicamba, dichlorprop-P, diclosulam,diuron, florasulam, flucarbazone-sodium, flumetsulam, fluroxypyr,glyphosate, glufosinate, imazamox, imazapyr, imazapic, imazaquin,imazethapyr, imazamethabenz, indaziflam, ioxynil, MCPA, mecoprop-P,metsulfuron-methyl, oxyfluorfen, penoxsulam, picloram, pinoxaden,pyroxsulam, rimsulfuron, sulfometuron, thifensulfuron-methyl,tebuthiuron, tribenuron-methyl, triclopyr, or agriculturally acceptablesalts or esters or mixtures thereof). The additional pesticide caninclude 2,4-D choline salt, triclopyr choline salt, or a mixturethereof. In some embodiments, the composition is free of naptalam andsalts and esters thereof. In some embodiments, the composition furthercomprises a herbicidal safener, an agriculturally acceptable adjuvant orcarrier, or a combination thereof.

The present disclosure also relates to methods of controllingundesirable vegetation, which comprise applying to vegetation or an areaadjacent the vegetation or applying to soil or water to prevent theemergence or growth of vegetation (a) aminocyclopyrachlor, or anagriculturally acceptable salt or ester thereof and (b) clopyralid, oran agriculturally acceptable salt or ester thereof, wherein (a) and (b)are each added in an amount sufficient to produce a synergisticherbicidal effect. In some embodiments, (a) and (b) are appliedsimultaneously. In some embodiments, (a) and (b) are appliedpostemergence to the undesirable vegetation. The undesirable vegetationcan be controlled in, for instance, sugar beets, sugar cane, canola oroilseed rape, fodder brassicas, corn or maize, mint, oats, wheat,barley, rice, spinach, turnips, cereals, CRP, trees and vines, grassesgrown for seed, pastures, grasslands, rangelands, IVM, fallow land,forestry, wildlife management areas, rights of way, or turf. In someembodiments, the undesirable vegetation is a broadleaf weed. Theundesirable vegetation can be controlled in crops tolerant toglyphosate, glufosinate, dicamba, phenoxy auxins, pyridyloxy auxins,aryloxyphenoxypropionates, acetyl CoA carboxylase (ACCase) inhibitors,imidazolinone, acetolactate synthase (ALS) inhibitors,4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors,protoporphyrinogen oxidase (PPO) inhibitors, triazines, bromoxynil, orcombinations thereof. For example, the undesired vegetation can becontrolled in phenoxy acid tolerant crops and the phenoxy acid tolerantcrops have tolerance conferred by an AAD12 gene. In some embodiments,the undesirable vegetation is resistant to auxinic herbicides. In someembodiments, (a) is applied in an amount of from 8-240 grams of acidequivalent per hectare (g ae/ha). In some embodiments, (b) is applied inan amount of from 20-560 g ae/ha.

The description below sets forth details of one or more embodiments ofthe present disclosure. Other features, objects, and advantages will beapparent from the description and from the claims.

DETAILED DESCRIPTION

The present disclosure relates to herbicidal compositions comprising asynergistically herbicidal effective amount of (a) aminocyclopyrachlor,or an agriculturally acceptable salt or ester thereof, and (b)clopyralid, or an agriculturally acceptable salt or ester thereof. Thepresent disclosure also relates to methods for controlling undesirablevegetation.

The term “herbicide,” as used herein, means an active ingredient thatkills, controls, or otherwise adversely modifies the growth ofvegetation. A “herbicidally effective amount” is an amount of an activeingredient that causes a “herbicidal effect,” i.e., an adverselymodifying effect and includes deviations from, for instance, naturaldevelopment, killing, regulation, desiccation, and retardation. Theterms “plants” and “vegetation” can include, for instance, germinantseeds, emerging seedlings, and established vegetation.

Aminocyclopyrachlor

Compositions and methods of the present disclosure can includeaminocyclopyrachlor or an agriculturally acceptable salt or esterthereof. Aminocyclopyrachlor, shown below, is a herbicide that can beused to control broadleaf weeds in, for instance, lawns (e.g.,residential, industrial, and institutional), golf courses, parks,cemeteries, athletic fields, sod farms, range and pasture,rights-of-way, roadsides, and other crop and non-crop uses. Itsherbicidal activity is described in The Pesticide Manual, FifteenthEdition, 2009.

In some embodiments, the aminocyclopyrachlor is in acid form and is6-amino-5-chloro-2-cyclopropylpyrimidine-4-carboxylic acid(6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid). In someembodiments, the aminocyclopyrachlor is in the form of an agriculturallyacceptable salt or ester thereof. Exemplary agriculturally acceptablesalts or esters of aminocyclopyrachlor include, but are not limited to,sodium salts, potassium salts, ammonium salts or substituted ammoniumsalts (e.g., mono-, di- and tri-C₁-C₈-alkylammonium salts such as methylammonium, dimethylammonium and isopropylammonium, mono-, di- andtri-hydroxy-C₂-C₈-alkylammonium salts such as hydroxyethylammonium,di(hydroxyethyl)ammonium, tri(hydroxyethyl)ammonium,hydroxypropylammonium, di(hydroxypropyl)ammonium andtri(hydroxypropyl)ammonium salts), and their diglycolamine salts andtheir esters (e.g., its C₁-C₈-alkyl esters and C₁-C₄-alkoxy-C₂-C₄-alkylesters, such as methyl esters, ethyl esters, isopropyl, butyl, hexyl,heptyl, isoheptyl, isooctyl, 2-ethylhexyl and butoxyethyl esters, andaryl esters such as benzyl). Exemplary agriculturally acceptable saltsof aminocyclopyrachlor can include aminocyclopyrachlor-sodium,aminocyclopyrachlor-potassium, or mixtures thereof. An exemplaryagriculturally acceptable ester of aminocyclopyrachlor can includeaminocyclopyrachlor-methyl. Aminocyclopyrachlor or agriculturallyacceptable salts or esters thereof are or have been commerciallyavailable, for example, from DuPont Crop Protection under the trademarksIMPRELIS®, STREAMLINE®, PERSPECTIVE®, VIEWPOINT®, METHOD®, REJUVRA®,INVORA®, and PLAINVIEW®.

The aminocyclopyrachlor or an agriculturally acceptable salt or esterthereof can be applied to vegetation or an area adjacent the vegetationor applied to soil or water to prevent the emergence or growth ofvegetation in an amount sufficient to induce a herbicidal effect. Insome embodiments, the aminocyclopyrachlor or agriculturally acceptablesalt or ester thereof is applied to vegetation or an area adjacent thevegetation or applied to soil or water to prevent the emergence orgrowth of vegetation in an amount of 8 grams or greater of acidequivalent per hectare (g ae/ha) (e.g., 10 g ae/ha or greater, 15 gae/ha or greater, 20 g ae/ha or greater, 25 g ae/ha or greater, 30 gae/ha or greater, 35 g ae/ha or greater, 40 g ae/ha or greater, 45 gae/ha or greater, 50 g ae/ha or greater, 55 g ae/ha or greater, 60 gae/ha or greater, 65 g ae/ha or greater, or 70 g ae/ha or greater). Insome embodiments, the aminocyclopyrachlor or agriculturally acceptablesalt or ester thereof is applied to vegetation or an area adjacent thevegetation or applied to soil or water to prevent the emergence orgrowth of vegetation in an amount of 240 g ae/ha or less (e.g., 230 gae/ha or less, 220 g ae/ha or less, 210 g ae/ha or less, 200 g ae/ha orless, 190 g ae/ha or less, 180 g ae/ha or less, 170 g ae/ha or less, 160g ae/ha or less, 150 g ae/ha or less, 140 g ae/ha or less, 130 g ae/haor less, 120 g ae/ha or less, 110 g ae/ha or less, 100 g ae/ha or less,90 g ae/ha or less, 80 g ae/ha or less, 70 g ae/ha or less, 60 g ae/haor less, 50 g ae/ha or less, 40 g ae/ha or less, 30 g ae/ha or less, 25g ae/ha or less, 20 g ae/ha or less, or 15 g ae/ha or less). In someembodiments, the aminocyclopyrachlor or agriculturally acceptable saltor ester thereof is applied to vegetation or an area adjacent thevegetation or applied to soil or water to prevent the emergence orgrowth of vegetation in an amount of from 8-240 g ae/ha (e.g., from9-220 g ae/ha, from 10-200 g ae/ha, from 11-180 g ae/ha, from 12-160 gae/ha, from 13-140 g ae/ha, from 14-120 g ae/ha, from 15-100 g ae/ha,from 16-80 g ae/ha, from 17-60 g ae/ha, or from 18-40 g ae/ha).

Clopyralid

Compositions and methods of the present disclosure can includeclopyralid or an agriculturally acceptable salt or ester thereof.Clopyralid (i.e., 3,6-dichloropicolinic acid;3,6-dichloro-2-pyridinecarboxylic acid), shown below, is a herbicidethat can be used to control broadleaf weeds in, for instance, cerealcrops, ornamentals, pastures, fallow, turf, rangelands, forest, andindustrial applications. Its herbicidal activity is described in ThePesticide Manual, Fifteenth Edition, 2009.

Clopyralid can be provided in its acid form (as shown above), or as anagriculturally acceptable salt or ester thereof. Exemplaryagriculturally acceptable salts or esters of clopyralid include, but arenot limited to, sodium salts, potassium salts, ammonium salts orsubstituted ammonium salts, in particular mono-, di- andtri-C₁-C₈-alkylammonium salts such as methyl ammonium, dimethylammoniumand isopropylammonium, mono-, di- and tri-hydroxy-C2-C8-alkylammoniumsalts such as hydroxyethylammonium, di(hydroxyethyl)ammonium,tri(hydroxyethyl)ammonium, hydroxypropylammonium,di(hydroxypropyl)ammonium and tri(hydroxypropyl)ammonium salts, theirdiglycolamine salts and their esters, in particular its C₁-C₈-alkylesters and C₁-C₄-alkoxy-C₂-C₄-alkyl esters, such as methyl esters, ethylesters, isopropyl, butyl, hexyl, heptyl, isoheptyl, isooctyl,2-ethylhexyl and butoxyethyl esters; and aryl esters such as benzyl.Exemplary agriculturally acceptable salts or esters of clopyralid caninclude clopyralid-potassium, clopyralid-olamine,clopyralid-tris(2-hydroxypropyl) ammonium, clopyralid-methyl, andmixtures thereof. In some embodiments, the clopyralid is provided as anamine salt, such as clopyralid-olamine salt, dimethylamine (DMA) salt,monoethanolamine (MEA) salt, triisopropanolamine (TIPA) salt, or amixture thereof. Clopyralid and agriculturally acceptable salts oresters thereof are or have been commercially available, for example,under the trademarks LONTREL® (by Dow AGROSCIENCES LLC), RECLAIM® (byDow AGROSCIENCES LLC), DOW SHIELD® (by Dow AGROSCIENCES LLC), STINGER®(by Dow AGROSCIENCES LLC), TRANSLINE® (by Dow AGROSCIENCES LLC),CURTAIL®, CONFRONT®, REDEEM®, FETREL® (by FERTIAGRO PTE. LTD.), CLEANSLATE® (by NUFARM AMERICAS INC.), GARRISON® (by NUFARM AMERICAS INC.),PHAETON® (by HEKTAS TICARET T.A.S.), CLOPYR® (by UNITED PHOSPHOROUSLTD.), CLEO® (by PARIJAT), WOPRO-CLOPYRALID® (by B.V. INDUSTRIE- &HANDELSONDERNEMING SIMONIS), BOSS® (by STOCKTON AGRIMOR AG), PIRATE® (byWILLOWOOD LTD.), TRELAN® (by WILLOWOOD LTD.), and TANGO® (by ZELAMLTD.).

The clopyralid or an agriculturally acceptable salt or ester thereofdescribed herein can be used in an amount sufficient to induce aherbicidal effect. In some embodiments, the clopyralid or agriculturallyacceptable salt or ester thereof is applied to vegetation or an areaadjacent the vegetation or applied to soil or water to prevent theemergence or growth of vegetation in an amount of 20 grams or greater ofacid equivalent per hectare (g ae/ha) (e.g., 30 g ae/ha or greater, 40 gae/ha or greater, 50 g ae/ha or greater, 60 g ae/ha or greater, 70 gae/ha or greater, 80 g ae/ha or greater, 90 g ae/ha or greater, 100 gae/ha or greater, 110 g ae/ha or greater, 120 g ae/ha or greater, 130 gae/ha or greater, 140 g ae/ha or greater, 160 g ae/ha or greater, 180 gae/ha or greater, 200 g ae/ha or greater, 250 g ae/ha or greater, 300 gae/ha or greater, or 350 g ae/ha or greater). In some embodiments, theclopyralid or agriculturally acceptable salt or ester thereof is appliedto vegetation or an area adjacent the vegetation or applied to soil orwater to prevent the emergence or growth of vegetation in an amount of560 g ae/ha or less (e.g., 530 g ae/ha or less, 500 g ae/ha or less, 470g ae/ha or less, 440 g ae/ha or less, 410 g ae/ha or less, 380 g ae/haor less, 350 g ae/ha or less, 320 g ae/ha or less, 290 g ae/ha or less,280 g ae/ha or less, 270 g ae/ha or less, 260 g ae/ha or less, 250 gae/ha or less, 240 g ae/ha or less, 230 g ae/ha or less, 220 g ae/ha orless, 210 g ae/ha or less, 200 g ae/ha or less, 190 g ae/ha or less, 180g ae/ha or less, 170 g ae/ha or less, 160 g ae/ha or less, 150 g ae/haor less, 140 g ae/ha or less, 130 g ae/ha or less, 120 g ae/ha or less,110 g ae/ha or less, 100 g ae/ha or less, 90 g ae/ha or less, 80 g ae/haor less, 70 g ae/ha or less, 60 g ae/ha or less, 50 g ae/ha or less, 40g ae/ha or less, or 30 g ae/ha or less). In some embodiments, theclopyralid or agriculturally acceptable salt or ester thereof is appliedto vegetation or an area adjacent the vegetation or applied to soil orwater to prevent the emergence or growth of vegetation in an amount offrom 20-560 g ae/ha (e.g., from 21-530 g ae/ha, from 22-500 g ae/ha,from 23-450 g ae/ha, from 24-400 g ae/ha, from 25-350 g ae/ha, from26-300 g ae/ha, from 27-250 g ae/ha, from 28-200 g ae/ha, from 29-175 gae/ha, from 30-150 g ae/ha, from 31-100 g ae/ha, from 32-80 g ae/ha, orfrom 35-70 g ae/ha).

Herbicidal Mixtures or Combinations

The (a) aminocyclopyrachlor or an agriculturally acceptable salt orester thereof is mixed with or applied in combination with (b)clopyralid or an agriculturally acceptable salt or ester thereof in anamount sufficient to induce a synergistic herbicidal effect. In someembodiments, (a) and (b) are used in an amount sufficient to induce asynergistic herbicidal effect while still showing good cropcompatibility (i.e., their use in crops does not result in increaseddamage to crops when compared to the individual application of theherbicidal compounds (a) or (b)). As described in the Herbicide Handbookof the Weed Science Society of America, Ninth Edition, 2007, p. 429,“‘synergism’ [is] an interaction of two or more factors such that theeffect when combined is greater than the predicted effect based on theresponse to each factor applied separately.” Synergistic in theherbicide context can mean that the use of (a) and (b) as defined aboveresults in an increased weed control effect compared to the weed controleffects that are possible with the use of (a) or (b) alone. In someembodiments, the damage or injury to the undesired vegetation caused bythe compositions and methods disclosed herein is evaluated using a scalefrom 0% to 100%, when compared with the untreated control vegetation,wherein 0% indicates no damage to the undesired vegetation and 100%indicates complete destruction of the undesired vegetation. In someembodiments, Colby's formula is applied to determine whether using (a)and (b) in combination shows a synergistic effect: S. R. Colby,Calculating Synergistic and Antagonistic Responses of HerbicideCombinations, WEEDS 15, p. 22 (1967)

wherein

$E = {X + Y - \frac{X*Y}{100}}$

X=effect in percent using (a) aminocyclopyrachlor or an agriculturallyacceptable salt or ester thereof at an application rate a;

Y=effect in percent using (b) clopyralid or an agriculturally acceptablesalt or ester thereof at an application rate b; and

E=expected effect (in %) of (a)+(b) at application rates a and b.

In Colby's equation, the value E corresponds to the effect (plant damageor injury) that is to be expected if the activity of the individualcompounds is additive. If the observed effect is higher than the value Ecalculated according to the Colby equation, then a synergistic effect ispresent according to the Colby equation.

In some embodiments, the compositions and methods disclosed herein aresynergistic as defined by the Colby equation. In some embodiments, thejoint action of aminocyclopyrachlor or an agriculturally acceptable saltor ester thereof and clopyralid or an agriculturally acceptable salt orester thereof results in enhanced activity against undesired vegetation(via synergism), even at application rates below those typically usedfor the pesticide to have a herbicidal effect on its own. In someembodiments, the compositions and methods disclosed herein can, based onthe individual components, be used at lower application rates to achievea herbicidal effect comparable to the effect produced by the individualcomponents at normal application rates. In some embodiments, thecompositions and methods disclosed herein provide an accelerated actionon undesired vegetation (i.e., they effect damaging of undesiredvegetation more quickly compared with application of the individualherbicides).

In some embodiments, the acid equivalent weight ratio of (a)aminocyclopyrachlor or agriculturally acceptable salt or ester thereofto (b) clopyralid or an agriculturally acceptable salt or ester thereofthat is sufficient to induce a synergistic herbicidal effect is at least1:70 (e.g., at least 1:65, at least 1:60, at least 1:55, at least 1:50,at least 1:45, at least 1:40, at least 1:35, at least 1:30, at least1:26, at least 1:22, at least 1:19, at least 1:17, at least 1:15, atleast 1:13, at least 1:11, at least 1:9, at least 1:7, at least 1:6, atleast 1:5, at least 1:4, at least 1:3, at least 1:2, at least 1:1, atleast 2:1, at least 3:1, at least 4:1, at least 5:1, at least 6:1, atleast 7:1, at least 8:1, at least 9:1, at least 10:1, or at least 11:1).In some embodiments, the acid equivalent weight ratio of (a) to (b) thatis sufficient to induce a synergistic herbicidal effect is 12:1 or less(e.g., 11:1 or less, 10:1 or less, 9:1 or less, 8:1 or less, 7:1 orless, 6:1 or less, 5:1 or less, 4:1 or less, 3:1 or less, 2:1 or less,1:1 or less, 1:2 or less, 1:3 or less, 1:4 or less, 1:5 or less, 1:6 orless, 1:7 or less, 1:8 or less, 1:9 or less, 1:10 or less, 1:15 or less,1:20 or less, 1:25 or less, 1:30 or less, 1:35 or less, 1:40 or less,1:45 or less, 1:50 or less, 1:60 or less). In some embodiments, the acidequivalent weight ratio of (a) to (b) is from 1:70 to 12:1 (e.g., from1:55 to 10:1, from 1:37 to 8:1, from 1:20 to 6:1, from 1:15 to 4:1, from1:12 to 2:1, from 1:8 to 1:1, from 1:6 to 2:3, or from 1:4 to 1:2).

Formulations

The present disclosure also relates to formulations of the compositionsand methods disclosed herein. In some embodiments, the formulation canbe in the form of a single package formulation including both (a)aminocyclopyrachlor or an agriculturally acceptable salt or esterthereof and (b) clopyralid or an agriculturally acceptable salt or esterthereof. In some embodiments, the formulation can be in the form of asingle package formulation including both (a) and (b) and furtherincluding at least one additive. In some embodiments, the formulationcan be in the form of a two-package formulation, wherein one packagecontains (a) and optionally at least one additive while the otherpackage contains (b) and optionally at least one additive. In someembodiments of the two-package formulation, the formulation including(a) and optionally at least one additive and the formulation including(b) and optionally at least one additive are mixed before applicationand then applied simultaneously. In some embodiments, the mixing isperformed as a tank mix (i.e., the formulations are mixed immediatelybefore or upon dilution with water), a pre-mix or a co-pack. In someembodiments, the formulation including (a) and the formulation including(b) are not mixed but are applied sequentially (in succession), forexample, immediately or within 1 hour, within 2 hours, within 4 hours,within 8 hours, within 16 hours, within 24 hours, within 2 days, orwithin 3 days, of each other.

In some embodiments, the formulation of (a) and (b) is present insuspended, emulsified, or dissolved form. Exemplary formulationsinclude, but are not limited to, aqueous solutions, powders,suspensions, also highly-concentrated aqueous, oily or other suspensionsor dispersions, aqueous emulsions, aqueous microemulsions, aqueoussuspo-emulsions, oil dispersions, pastes, dusts, and materials forspreading or granules.

In some embodiments, (a) aminocyclopyrachlor or an agriculturallyacceptable salt or ester thereof and/or (b) clopyralid or anagriculturally acceptable salt or ester thereof is an aqueous solutionthat can be diluted before use. In some embodiments, (a) and/or (b) isprovided as a high-strength formulation such as a concentrate. In someembodiments, the concentrate is stable and retains potency duringstorage and shipping. In some embodiments, the concentrate is a clear,homogeneous liquid that is stable at temperatures of 54° C. or greater.In some embodiments, the concentrate does not exhibit any precipitationof solids at temperatures of −10° C. or higher. In some embodiments, theconcentrate does not exhibit separation, precipitation, orcrystallization of any components at low temperatures. For example, theconcentrate remains a clear solution at temperatures below 0° C. (e.g.,below −5° C., below −10° C., below −15° C.). In some embodiments, theconcentrate exhibits a viscosity of less than 50 centipoise (50megapascals), even at temperatures as low as 5° C.

The compositions and methods disclosed herein can also be mixed with orapplied with an additive. In some embodiments, the additive can bediluted in water or can be concentrated. In some embodiments, theadditive is added sequentially. In some embodiments, the additive isadded simultaneously. In some embodiments, the additive is premixed withthe aminocyclopyrachlor or agriculturally acceptable salt or esterthereof. In some embodiments, the additive is premixed with theclopyralid or agriculturally acceptable salt or ester thereof. In someembodiments, the additive is premixed with the aminocyclopyrachlor oragriculturally acceptable salt or ester and the clopyralid oragriculturally acceptable salt or ester thereof.

In some embodiments, the additive is an additional pesticide. Exemplaryadditional pesticides include, but are not limited to, 2,4-D,acetochlor, aclonifen, amicarbazone, 4-aminopicolinic acid basedherbicides, such as those described in U.S. Pat. Nos. 7,314,849 (B2) and7,432,227 (B2), amidosulfuron, aminopyralid, aminotriazole, ammoniumthiocyanate, asulam, atrazine, beflubutamid, benazolin, bentazone,bifenox, bromacil, bromoxynil, butachlor, butafenacil, butralin,butroxydim, carbetamide, carfentrazone, carfentrazone-ethyl,chlormequat, chlorsulfuron, chlortoluron, cinidon-ethyl, clethodim,clodinafop-propargyl, clomazone, cyanazine, cyclosulfamuron, cycloxydim,dicamba, dichlobenil, dichlorprop-P, diclofop-methyl, diclosulam,diflufenican, diflufenzopyr, dimefuron, dimethachlor, diquat, diuron,EPTC, ET-751, ethoxysulfuron, fenoxaprop, fenoxaprop-ethyl,fenoxaprop-ethyl+isoxidifen-ethyl, fenoxaprop-p-ethyl, fenoxasulfone,flazasulfuron, florasulam, fluazifop, fluazifop-P-butyl, flucarbazone,flucabazone-sodium, flucetosulfuron (LGC-42153), flufenacet,flumetsulam, flumioxacin, flupyrsulfuron, fluroxypyr, fluroxypyr-meptyl,flurtamone, glufosinate, glufosinate-ammonium, glyphosate,haloxyfop-methyl, haloxyfop-R, hexazinone, imazamethabenz, imazamox,imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indanofan,indaziflam, iodosulfuron, iodosulfuron-ethyl-sodium, ioxynil,isoproturon, isoxaben, isoxaflutole, lactofen, linuron, MCPA, MCPB,mecoprop-P, mesosulfuron, mesosulfuron-ethyl sodium, metazochlor,metosulam, metribuzin, metsulfuron, metsulfuron-methyl, MSMA,napropamide, norfurazon, orthosulfamuron, oryzalin, oxadiargyl,oxadiazon, oxyfluorfen, paraquat, pendimethalin, penoxsulam, picloram,picolinafen, pinoxaden, primisulfuron, profluazol, propaquizafop,propoxycarbazone, propyzamide, prosulfocarb, prosulfuron, pyraflufenethyl, pyrasulfotole, pyribenzoxim (LGC-40863), pyroxsulam,pyroxasulfone, quinmerac, quizalofop-ethyl-D, quizalofop-P-ethyl,quizalofop-p-tefuryl, rimsulfuron, sethoxydim, simazine, sulfentrazone,sulfometuron, sulfosate, sulfosulfuron, tebuthiuron, tepraloxidim,terbacil, terbutryn, thiazopyr, thifensulfuron, thifensulfuron-methyl,topramezone, tralkoxydim, triasulfuron, tribenuron, tribenuron-methyl,triafamone, triclopyr, and trifluralin, and agriculturally acceptablesalts, esters and mixtures thereof. In some embodiments, the additionalpesticide includes 2,4-D choline salt, triclopyr choline salt, or amixture thereof.

In some embodiments, the compositions and methods disclosed herein donot incorporate naptalam (i.e., N-1-naphthylphthalamic acid or NPA) orthe salts or esters thereof. In some embodiments, the compositions andmethods disclosed herein are free of naptalam or the salts or estersthereof. In some embodiments, naptalam or the salts or esters thereofare not applied to the vegetation, the area adjacent to the vegetation,the soil, or the water, in the methods disclosed herein.

In some embodiments, the aminocyclopyrachlor or an agriculturallyacceptable salt or ester thereof is provided in a premixed formulationwith an additional pesticide. In some embodiments, theaminocyclopyrachlor or an agriculturally acceptable salt or esterthereof is premixed with, chlorsulfuron, dicamba, imazapyr, glufosinate,glyphosate, MCPA, metsulfuron-methyl, sulfometuron, or mixtures thereof.Exemplary premixes of aminocyclopyrachlor or an agriculturallyacceptable salt or ester thereof and an additive that are or have beencommercially available include, but are not limited to, PERSPECTIVE® (apremix incorporating chlorsulfuron by DUPONT CROP PROTECTION),VIEWPOINT® (a premix incorporating imazapyr and metsulfuron-methyl byDUPONT CROP PROTECTION), PLAINVIEW® (a premix incorporating sulfometuronand chlorsulfuron by DUPONT CROP PROTECTION), or STREAMLINE® (a premixincorporating metsulfuron-methyl by DUPONT CROP PROTECTION).

In some embodiments, the clopyralid or an agriculturally acceptable saltor ester thereof is provided in a premixed formulation with anadditional pesticide. In some embodiments, the clopyralid or anagriculturally acceptable salt or ester thereof is premixed withacetochlor, benazolin, bensulfuron-methyl, 2,4-D, dicamba, flumetsulam,fluroxypyr, glufosinate, glyphosate, imazamethabenz, imazamox, imazapic,imazapyr, imazaquin, imazethapyr, imazosulfuron, MCPA, triclopyr, ormixtures thereof. Exemplary premixes of clopyralid or an agriculturallyacceptable salt or ester thereof and an additive that are or have beencommercially available include, but are not limited to, CURTAIL® (apremix incorporating 2,4-D by Dow AGROSCIENCES LLC), MILLENIUM ULTRA 2 ®(a premix incorporating 2,4-D and dicamba by NUFARM AMERICAS INC.),SURESTART® (a premix incorporating acetochlor and flumetsulam by DOWAGROSCIENCES LLC), BENAZALOX® (a premix incorporating benazolin by BAYERCROPSCIENCE), KE CAOTE® (a premix incorporating bensulfuron-methyl byNANJING RED SUN CO., LTD.), HORNET® (a premix incorporating flumetsulamby DOW AGROSCIENCES LLC), WIDEMATCH® (a premix incorporating fluroxypyrby DOW AGROSCIENCES LLC), HAT TRICK® (a premix incorporating fluroxypyrand MCPA by LOVELAND PRODS., INC.), CURTAIL M® (a premix incorporatingMCPA by Dow AGROSCIENCES LLC), CONFRONT® (a premix incorporatingtriclopyr by DOW AGROSCIENCES LLC), and REDEEM® (a premix incorporatingtriclopyr by Dow AGROSCIENCES LLC).

In some embodiments, the additive includes an agriculturally acceptableadjuvant. Exemplary agriculturally acceptable adjuvants include, but arenot limited to, antifreeze agents, antifoam agents, compatibilizingagents, sequestering agents, neutralizing agents and buffers, corrosioninhibitors, colorants, odorants, penetration aids, wetting agents,spreading agents, dispersing agents, thickening agents, freeze pointdepressants, antimicrobial agents, crop oil, safeners, adhesives (forinstance, for use in seed formulations), surfactants, protectivecolloids, emulsifiers, tackifiers, and mixtures thereof. Exemplaryagriculturally acceptable adjuvants include, but are not limited to,crop oil concentrate (mineral oil (85%) +emulsifiers (15%)) or less,nonylphenol ethoxylate or less, benzylcocoalkyldimethyl quaternaryammonium salt or less, blend of petroleum hydrocarbon, alkyl esters,organic acid, and anionic surfactant or less, C₉-C₁₁ alkylpolyglycosideor less, phosphate alcohol ethoxylate or less, natural primary alcohol(C₁₂-C₁₆) ethoxylate or less, di-sec-butylphenol EO-PO block copolymeror less, polysiloxane-methyl cap or less, nonylphenol ethoxylate+ureaammonium nitrate or less, emulsified methylated seed oil or less,tridecyl alcohol (synthetic) ethoxylate (8 EO) or less, tallow amineethoxylate (15 EO) or less, and PEG(400) dioleate-99.

In some embodiments, the additive is a safener that is an organiccompound leading to better crop plant compatibility when applied with aherbicide. In some embodiments, the safener itself is herbicidallyactive. In some, the safener acts as an antidote or antagonist in thecrop plants and can reduce or prevent damage to the crop plants.Exemplary safeners include, but are not limited to, AD-67 (MON 4660),benoxacor, benthiocarb, brassinolide, cloquintocet (mexyl), cyometrinil,cyprosulfamide, daimuron, dichlormid, dicyclonon, dietholate,dimepiperate, disulfoton, fenchlorazole, fenchlorazole-ethyl, fenclorim,flurazole, fluxofenim, furilazole, harpin proteins, isoxadifen-ethyl,jiecaowan, jiecaoxi, mefenpyr, mefenpyr-diethyl, mephenate, naphthalicanhydride, 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine,4-(dichloroacetyl)-1-oxa-4-azaspiro [4.5]decane, oxabetrinil, 829148,and N-phenyl-sulfonylbenzoic acid amides, as well as thereofagriculturally acceptable salts and, provided they have a carboxylgroup, their agriculturally acceptable derivatives. In some embodiments,the safener can be cloquintocet or an ester or salt thereof, such ascloquintocet (mexyl). For example, cloquintocet can be used toantagonize harmful effects of the compositions on rice and cereals.

Exemplary surfactants (e.g., wetting agents, tackifiers, dispersants,emulsifiers) include, but are not limited to, the alkali metal salts,alkaline earth metal salts and ammonium salts of aromatic sulfonicacids, for example lignosulfonic acids, phenolsulfonic acids,naphthalenesulfonic acids, and dibutylnaphthalenesulfonic acid, and offatty acids, alkyl- and alkylarylsulfonates, alkyl sulfates, laurylether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-,hepta- and octadecanols, and also of fatty alcohol glycol ethers,condensates of sulfonated naphthalene and its derivatives withformaldehyde, condensates of naphthalene or of the naphthalene sulfonicacids with phenol and formaldehyde, polyoxyethylene octylphenol ether,ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl ortributylphenyl polyglycol ether, alkyl aryl polyether alcohols,isotridecyl alcohol, fatty alcohol/ethylene oxide condensates,ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylenealkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters,lignosulfite waste liquors and proteins, denatured proteins,polysaccharides (e.g., methylcellulose), hydrophobically modifiedstarches, polyvinyl alcohol, polycarboxylates, polyalkoxylates,polyvinyl amine, polyethyleneimine, polyvinylpyrrolidone and copolymersthereof.

Exemplary thickeners include, but are not limited to, polysaccharides,such as xanthan gum, and organic and inorganic sheet minerals, andmixtures thereof

Exemplary antifoam agents include, but are not limited to, siliconeemulsions, long-chain alcohols, fatty acids, salts of fatty acids,organofluorine compounds, and mixtures thereof.

Exemplary antimicrobial agents include, but are not limited to,bactericides based on dichlorophen and benzyl alcohol hemiformal, andisothiazolinone derivates, such as alkylisothiazolinones andbenzisothiazolinones, and mixtures thereof.

Exemplary antifreeze agents, include, but are not limited to ethyleneglycol, propylene glycol, urea, glycerol, and mixtures thereof.

Exemplary colorants include, but are not limited to, the dyes knownunder the names Rhodamin B, pigment blue 15:4, pigment blue 15:3,pigment blue 15:2, pigment blue 15:1, pigment blue 80, pigment yellow 1,pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1,pigment red 57:1, pigment red 53:1, pigment orange 43, pigment orange34, pigment orange 5, pigment green 36, pigment green 7, pigment white6, pigment brown 25, basic violet 10, basic violet 49, acid red 51, acidred 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basicred 108, and mixtures thereof.

Exemplary adhesives include, but are not limited to,polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, tylose, andmixtures thereof.

In some embodiments, the additive includes a carrier. In someembodiments, the additive includes a liquid or solid carrier. In someembodiments, the additive includes an organic or inorganic carrier.Exemplary liquid carriers include, but are not limited to, petroleumfractions or hydrocarbons such as mineral oil, aromatic solvents,paraffinic oils, and the like or less, vegetable oils such as soybeanoil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconutoil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil,safflower oil, sesame oil, tung oil and the like or less, esters of theabove vegetable oils or less, esters of monoalcohols or dihydric,trihydric, or other lower polyalcohols (4-6 hydroxy containing), such as2-ethyl hexyl stearate, n-butyl oleate, isopropyl myristate, propyleneglycol dioleate, di-octyl succinate, di-butyl adipate, di-octylphthalate and the like or less, esters of mono, di and polycarboxylicacids and the like, toluene, xylene, petroleum naphtha, crop oil,acetone, methyl ethyl ketone, cyclohexanone, trichloroethylene,perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propyleneglycol monomethyl ether and diethylene glycol monomethyl ether, methylalcohol, ethyl alcohol, isopropyl alcohol, amyl alcohol, ethyleneglycol, propylene glycol, glycerine, N-methyl-2-pyrrolidinone,N,N-dimethyl alkylamides, dimethyl sulfoxide, liquid fertilizers and thelike, and water as well as mixtures thereof. Exemplary solid carriersinclude, but are not limited to, silicas, silica gels, silicates, talc,kaolin, limestone, lime, chalk, bole, loess, clay, dolomite,diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide,ground synthetic materials, pyrophyllite clay, attapulgus clay,kieselguhr, calcium carbonate, bentonite clay, Fuller's earth,cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnutshell flour, lignin, ammonium sulfate, ammonium phosphate, ammoniumnitrate, ureas, cereal meal, tree bark meal, wood meal and nutshellmeal, cellulose powders, and mixtures thereof.

In some embodiments, emulsions, pastes or oil dispersions, can beprepared by homogenizing (a) and (b) in water by means of wetting agent,tackifier, dispersant or emulsifier. In some embodiments, concentratessuitable for dilution with water are prepared, comprising (a), (b), awetting agent, a tackifier, and a dispersant or emulsifier.

In some embodiments, powders or materials for spreading and dusts can beprepared by mixing or concomitant grinding of (a) and (b) and optionallya safener with a solid carrier.

In some embodiments, granules (e.g. coated granules, impregnatedgranules and homogeneous granules) can be prepared by binding the (a)and (b) to solid carriers.

The formulations disclosed herein can comprise a synergistic,herbicidally effective amount of (a) and (b). In some embodiments, theconcentrations of (a) and (b) in the formulations can be varied. In someembodiments, the formulations comprise from 1% to 95% (e.g., from 5% to95%, from 10% to 80%, from 20% to 70%, from 30% to 50%) by total weightof (a) and (b). In some embodiments, (a) and (b), independently, can beemployed in a purity of from 90% to 100% (e.g., from 95% to 100%)according to NMR spectrometry. In some embodiments, the concentrationsof (a), (b), and additional pesticides in the formulations can bevaried. In some embodiments, the formulations comprise from 1% to 95%(e.g., from 5% to 95%, from 10% to 80%, from 20% to 70%, from 30% to50%) by total weight of (a), (b), and additional pesticides. In someembodiments, (a), (b), and additional pesticides, independently, can beemployed in a purity of from 90% to 100% (e.g., from 95% to 100%)according to NMR spectrometry.

Methods of Application

The compositions disclosed herein can be applied in any known techniquefor applying herbicides. Exemplary application techniques include, butare not limited to, spraying, atomizing, dusting, spreading, or directapplication to the vegetation, to the soil, or into water (in-water).The method of application can vary depending on the intended purpose. Insome embodiments, the method of application can be chosen to ensure thefinest possible distribution of the compositions disclosed herein.

The compositions disclosed herein can be applied pre-emergence (beforethe emergence of undesirable vegetation) or post-emergence (i.e., duringand/or after emergence of the undesirable vegetation). In someembodiments, the compositions disclosed herein are appliedpost-emergence when the undesirable vegetation starts with leafdevelopment up to flowering. In some embodiments, the compositionsdisclosed herein are applied post-emergence to relatively immatureundesirable vegetation to achieve the maximum control of weeds. In someembodiments when the compositions are used in crops, the compositionscan be applied after seeding and before or after the emergence of thecrop plants. In some embodiments, the compositions disclosed herein showgood crop tolerance even when the crop has already emerged, and can beapplied during or after the emergence of the crop plants. In someembodiments, when the compositions are used in crops, the compositionscan be applied before seeding of the crop plants.

In some embodiments, the compositions disclosed herein are applied tovegetation or an area adjacent the vegetation or applying to soil orwater to prevent the emergence or growth of vegetation by spraying(e.g., foliar spraying). In some embodiments, the spraying techniquesuse, for example, water as carrier and spray liquor rates of from 2liters per hectare (L/ha) to 2000 L/ha (e.g., from 10 L/ha to 2000 L/ha,from 50 L/ha to 1000 L/ha, or from 100 to 5001/ha). In some embodiments,the compositions disclosed herein are applied by the low-volume or theultra-low-volume method, wherein the application is in the form of microgranules. In some embodiments, wherein the compositions disclosed hereinare less well tolerated by certain crop plants, the compositions can beapplied with the aid of the spray apparatus in such a way that they comeinto little contact, if any, with the leaves of the sensitive cropplants while reaching the leaves of undesirable vegetation that growsunderneath or the bare soil (e.g., post-directed or lay-by).

In some embodiments, wherein the undesirable vegetation is treatedpost-emergence, the compositions disclosed herein are applied by foliarapplication. In some embodiments, herbicidal activity is exhibited bythe compounds of the synergistic mixture when they are applied directlyto the plant or to the locus of the plant at any stage of growth orbefore planting or emergence. The effect observed can depend upon thetype of undesirable vegetation to be controlled, the stage of growth ofthe undesirable vegetation, the application parameters of dilution andspray drop size, the particle size of solid components, theenvironmental conditions at the time of use, the specific compoundemployed, the specific adjuvants and carriers employed, the soil type,and the like, as well as the amount of chemical applied. In someembodiments, these and other factors can be adjusted to promotenon-selective or selective herbicidal action.

The compositions and methods disclosed herein can be used to controlundesired vegetation in a variety of crop and non-crop applications. Insome embodiments, the compositions and methods disclosed herein can beused for controlling undesired vegetation in crops. Exemplary cropsinclude, but are not limited to, sugar beets or less, mint or less,spinach or less, turnips or less, cereals such as wheat and wheat-likecrops, rye, triticale and barley, corn, oats, maize, sorghum, rice, andsugar cane or less, pulse crops such as pea, bean and lentils or less,oilseed crops such as canola, oilseed rape and sunflower or less, fodderbrassicas or less, forage crops such as alfalfa and clover or less,cotton or less, and soybean. In some embodiments, the compositions andmethods disclosed herein can be used for controlling undesiredvegetation in non-crop areas. Exemplary non-crop areas include, but arenot limited to, turf, pasture, fallow, wildlife management areas, orrangeland. In some embodiments, the compositions and methods disclosedherein can be used in industrial vegetation management (IVM) or forutility, pipeline, roadside, and railroad rights-of-way applications. Insome embodiments, the compositions and methods disclosed herein can alsobe used in forestry (e.g., for site preparation or for combatingundesirable vegetation in plantation forests—“conifer or tree release”).In some embodiments, the compositions and methods disclosed herein canbe used to control undesirable vegetation in conservation reserveprogram lands (CRP), trees, vines, grasslands, and grasses grown forseeds. In some embodiments, the compositions and methods disclosedherein can be used on lawns (e.g., residential, industrial, andinstitutional), golf courses, parks, cemeteries, athletic fields, andsod farms.

The compositions and methods disclosed herein can also be used in cropplants that are resistant to, for instance, herbicides, pathogens,and/or insects. In some embodiments, the compositions and methodsdisclosed herein can be used in crop plants that are resistant to one ormore herbicides because of genetic engineering or breeding. In someembodiments, the compositions and methods disclosed herein can be usedin crop plants that are resistant to one or more pathogens such as plantpathogenous fungi owing to genetic engineering or breeding. In someembodiments, the compositions and methods disclosed herein can be usedin crop plants that are resistant to attack by insects owing to geneticengineering or breeding. Exemplary resistant crops include, but are notlimited to, corn (maize), sorghum, wheat, sunflower, rice, canola,oilseed rape, soybeans, cotton, alfalfa, clover, rye, barley, triticale,and sugarcane that are resistant to synthetic auxins, or crop plantsthat, owing to introduction of the gene for Bacillus thuringiensis (orBt) toxin by genetic modification, are resistant to attack by certaininsects. In some embodiments, the compositions and methods describedherein also can be used in conjunction with glyphosate, glufosinate,dicamba, phenoxy auxins, pyridyloxy auxins, aryloxyphenoxypropionates,acetyl CoA carboxylase (ACCase) inhibitors, imidazolinones, acetolactatesynthase (ALS) inhibitors, 4-hydroxyphenyl-pyruvate dioxygenase (HPPD)inhibitors, protoporphyrinogen oxidase (PPO) inhibitors, triazines, andbromoxynil to control vegetation in crops tolerant to glyphosate,glufosinate, dicamba, phenoxy auxins, pyridyloxy auxins,aryloxyphenoxypropionates, acetyl CoA carboxylase (ACCase) inhibitors,imidazolinones, acetolactate synthase (ALS) inhibitors,4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors,protoporphyrinogen oxidase (PPO) inhibitors, triazines, bromoxynil, orcombinations thereof. In some embodiments, the undesirable vegetation iscontrolled in glyphosate, glufosinate, dicamba, phenoxy auxins,pyridyloxy auxins, aryloxyphenoxypropionates, acetyl CoA carboxylase(ACCase) inhibitors, imidazolinones, acetolactate synthase (ALS)inhibitors, 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors,protoporphyrinogen oxidase (PPO) inhibitors, triazines, and bromoxyniltolerant crops possessing multiple or stacked traits conferringtolerance to multiple chemistries and/or multiple modes of action. Insome embodiments, the undesired vegetation is controlled in phenoxy acidtolerant crops and the phenoxy acid tolerant crops have toleranceconferred by an AAD12 gene. The combination of (a), (b), and acomplementary herbicide or salt or ester thereof can be used incombination with herbicides that are selective for the crop beingtreated and which complement the spectrum of weeds controlled by thesecompounds at the application rate employed.

The herbicidal compositions prepared disclosed herein are effectiveagainst a variety of types of undesirable vegetation. In someembodiments, the compositions disclosed herein can be used forcontrolling broadleaf weeds. Exemplary broadleaf weeds include, but arenot limited to, Polygonum species such as wild buckwheat (Polygonumconvolvolus), Amaranthus species such as pigweed (Amaranthusretroflexus), Chenopodium species such as common lambsquarters(Chenopodium album L.), Sida species such as prickly sida (Sida spinosaL.), Ambrosia species such as common ragweed (Ambrosia artemisiifolia),Acanthospermum species, Anthemis species, Atriplex species, Cirsiumspecies, Convolvulus species, Conyza species, such as horseweed (Conyzacanadensis), Cassia species, Commelina species, Datura species,Euphorbia species, Geranium species, Galinsoga species, morning-glory(Ipomoea species), Lamium species, Malva species, Matricaria species,Prosopis species, Rumex species, Sysimbrium species, Solanum species,Trifolium species, Xanthium species, Veronica species, Viola species,common chickweed (Stella ria media), velvetleaf (Abutilon theophrasti),Hemp sesbania (Sesbania exaltata Cory), Anoda cristata, Bidens pilosa,Brassica kaber, Capsella bursa-pastoris, Centaurea cyanus, Galeopsistetrahit, Galium aparine, Helianthus annuus, Desmodium tortuosum, Bassiascoparia, Medicago arabica, Mercurialis annua, Myosotis arvensis,Papaver rhoeas, Raphanus raphanistrum, Salsola species, Sinapisarvensis, Sonchus arvensis, Thlaspi arvense, Tagetes minuta, Richardiabrasiliensis, Plantago major, and Plantago lanceolata. In someembodiments, the undesirable vegetation includes buckhorn plantain(Plantago lanceolata) or calvary clover (Medicago arabica). In someembodiments, the undesirable vegetation comprises a herbicide resistantor tolerant weed, wherein the resistant or tolerant weed is a biotypewith resistance or tolerance to multiple herbicides, multiple chemicalclasses, multiple herbicide modes-of-action or via multiple resistancemechanisms.

By way of non-limiting illustration, examples of certain embodiments ofthe present disclosure are given below.

EXAMPLES Evaluation of Aminocyclopyrachlor and Clopyralid-olamine forPost-Emergence Synergistic Weed Control

Field trials were conducted with applications made to establishedgrassland with naturally occurring weed populations. The target plantswere treated with postemergence foliar applications when they reachedthree to five inches tall. All treatments were applied using arandomized complete block trial design, with 4 replications pertreatment.

Treatments consisted of aminocyclopyrachlor in acid form andclopyralid-olamine, each in water and applied alone or in combination.Spray solutions were prepared using an appropriate amount of dilution toform a 2 L aqueous spray solution with active ingredients in single andtwo way combinations. Formulated compounds were applied to the plantmaterial with a backpack sprayer equipped with 8003 nozzles calibratedto deliver 187 L/ha at a spray height of 18 inches (43 centimeters (cm))above average plant canopy.

The treated plants were buckhorn plantain (Plantago lanceolata, PLALA)and calvary clover (Medicago arabica, MEDAB). The treated plots andcontrol plots were rated blind at various intervals after application.Ratings were based on a scale of 0-100%, as discussed above, wherein 0%indicates no damage to the undesired vegetation and 100% indicatescomplete destruction of the undesired vegetation

Colby's equation was used to determine the herbicidal effects expectedfrom the mixtures, as described above. The results were measured at 7days and 27 days after the first application of the compositions. Thetrials exhibited unexpected synergy, and those results were foundstatistically significant under the p-value test. The herbicide tank mixcombinations tested, application rates and ratios employed, plantspecies tested, and results are given below.

Aminocyclopyrachlor Clopyralid-olamine Combination Weed Evaluation gMean % weed g Mean % weed Measured Colby predicted Bayer Interval ae/hacontrol ae/ha control mean % weed control mean % weed control PLALA  7days 18 18.75 35 18 50 33.69 PLALA 27 days 18 22.5 70 28 70 44.75 PLALA27 days 35 35 70 28 92.5 51.75 MEDAB 27 days 18 27.5 35 13 77.5 37.12MEDAB 27 days 18 27.5 70 30 72.5 49.75

As shown above, the samples demonstrated synergistic weed control, withhigher measured weed control than would be predicted by the Colbyequation.

The compositions and methods of the appended claims are not limited inscope by the specific compositions and methods described herein, whichare intended as illustrations of a few aspects of the claims and anycompositions and methods that are functionally equivalent are intendedto fall within the scope of the claims. Various modifications of thecompositions and methods in addition to those shown and described hereinare intended to fall within the scope of the appended claims. Further,while only certain representative compositions and method stepsdisclosed herein are specifically described, other combinations of thecompositions and method steps also are intended to fall within the scopeof the appended claims, even if not specifically recited. Thus, acombination of steps, elements, components, or constituents may beexplicitly mentioned herein or less, however, other combinations ofsteps, elements, components, and constituents are included, even thoughnot explicitly stated. The term “comprising” and variations thereof asused herein is used synonymously with the term “including” andvariations thereof and are open, non-limiting terms. Although the terms“comprising” and “including” have been used herein to describe variousembodiments, the terms “consisting essentially of and “consisting of canbe used in place of “comprising” and “including” to provide for morespecific embodiments of the invention and are also disclosed. Other thanin the examples, or where otherwise noted, all numbers expressingquantities of ingredients, reaction conditions, and so forth used in thespecification and claims are to be understood at the very least, and notas an attempt to limit the application of the doctrine of equivalents tothe scope of the claims, to be construed in light of the number ofsignificant digits and ordinary rounding approaches.

What is claimed is:
 1. A herbicidal composition comprising asynergistically herbicidal effective amount of (a) aminocyclopyrachlor,or an agriculturally acceptable salt or ester thereof and (b)clopyralid, or an agriculturally acceptable salt or ester thereof. 2.The composition of claim 1, wherein (a) includes aminocyclopyrachlor inacid form.
 3. The composition of claim 1, wherein (b) includesclopyralid-olamine.
 4. The composition of claim 1, wherein the acidequivalent weight ratio of (a) to (b) is from 1:70 to 12:1.
 5. Thecomposition of claim 1, wherein the acid equivalent weight ratio of (a)to (b) is from 1:4 to 1:2.
 6. The composition of claim 1, furthercomprising an additional pesticide, wherein the additional pesticideincludes one or more pesticides selected from the group consisting ofaminopyralid, amicarbazone, bromoxynil, chlorsulfuron, 2,4-D, dicamba,dichlorprop-P, diclosulam, diuron, florasulam, flucarbazone-sodium,flumetsulam, fluroxypyr, glyphosate, glufosinate, imazamox, imazapyr,imazapic, imazaquin, imazethapyr, imazamethabenz, indaziflam, ioxynil,MCPA, mecoprop-P, metsulfuron-methyl, oxyfluorfen, penoxsulam, picloram,pinoxaden, pyroxsulam, rimsulfuron, sulfometuron, thifensulfuron-methyl,tebuthiuron, tribenuron-methyl, triclopyr, and agriculturally acceptablesalts or esters or mixtures thereof.
 7. The composition of claim 1,wherein the composition is provided as a herbicidal concentrate.
 8. Amethod of controlling undesirable vegetation, which comprises applyingto vegetation or an area adjacent the vegetation or applying to soil orwater to prevent the emergence or growth of vegetation (a)aminocyclopyrachlor, or an agriculturally acceptable salt or esterthereof and (b) clopyralid, or an agriculturally acceptable salt orester thereof, wherein (a) and (b) are each added in an amountsufficient to produce a synergistic herbicidal effect.
 9. The method ofclaim 8, wherein (a) and (b) are applied simultaneously.
 10. The methodof claim 8, wherein (a) and (b) are applied postemergence to theundesirable vegetation.
 11. The method of claim 8, wherein (a) includesaminocyclopyrachlor in acid form.
 12. The method of claim 8, wherein (b)includes clopyralid-olamine.
 13. The method of claim 8, furthercomprising applying an additional pesticide, wherein the additionalpesticide includes one or more pesticides selected from the groupconsisting of aminopyralid, amicarbazone, bromoxynil, chlorsulfuron,2,4-D, dicamba, dichlorprop-P, diclosulam, diuron, florasulam,flucarbazone-sodium, flumetsulam, fluroxypyr, glyphosate, glufosinate,imazamox, imazapyr, imazapic, imazaquin, imazethapyr, imazamethabenz,indaziflam, ioxynil, MCPA, mecoprop-P, metsulfuron-methyl, oxyfluorfen,penoxsulam, picloram, pinoxaden, pyroxsulam, rimsulfuron, sulfometuron,thifensulfuron-methyl, tebuthiuron, tribenuron-methyl, triclopyr, andagriculturally acceptable salts or esters or mixtures thereof.
 14. Themethod of claim 8, wherein the undesirable vegetation is controlled insugar beets, sugar cane, canola or oilseed rape, fodder brassicas, cornor maize, mint, oats, wheat, barley, rice, spinach, turnips, cereals,CRP, trees and vines, grasses grown for seed, pastures, grasslands,rangelands, IVM, forestry, fallow land, wildlife management areas,rights of way, or turf.
 15. The method of claim 8, wherein theundesirable vegetation is controlled in crops tolerant to glyphosate,glufosinate, dicamba, phenoxy auxins, pyridyloxy auxins,aryloxyphenoxypropionates, acetyl CoA carboxylase (ACCase) inhibitors,imidazolinones, acetolactate synthase (ALS) inhibitors,4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors,protoporphyrinogen oxidase (PPO) inhibitors, triazines, bromoxynil, orcombinations thereof.
 16. The method of claim 8, wherein the undesirablevegetation is controlled in phenoxy acid tolerant crops and the phenoxyacid tolerant crops have tolerance conferred by an AAD12 gene.
 17. Themethod of claim 8, wherein the undesirable vegetation is resistant toauxinic herbicides.
 18. The method of claim 8, wherein the undesirablevegetation includes buckhorn plantain or calvary clover.
 19. The methodof claim 8, wherein (a) is applied in an amount of from 8-240 g ae/ha.20. The method of claim 8, wherein (b) is applied in an amount of from20-560 g ae/ha.